JPH06287407A - Aqueous crosslinkable resin composition - Google Patents

Abstract

PURPOSE:To obtain an aqueous crosslinkable resin composition having excellent workability, easily handleable without causing gelatinization and easily crosslinkable at room temperature to give a crosslinked coating film having excellent water-resistance, water whitening resistance, blocking resistance, heat- resistance, solvent resistance, adhesivity and hardness and properly adjustable surface dryness. CONSTITUTION:The aqueous crosslinkable resin composition is composed of (A) an aqueous dispersion of a resin containing carbonyl group and composed of resin particles having two or more layers, wherein at least the outermost layer contains carbonyl group, (B) a hydrazine derivative having at least two hydrazino groups in the molecule and (C) an epoxy group-containing compound containing two or more epoxy groups in the molecule. At least 5wt.% of the outermost layer of the resin particle and 4-50wt.% of the total particle in the aqueous dispersion of the carbonyl-containing resin are present in solubilized state.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides a film which easily undergoes a crosslinking reaction at room temperature and, after crosslinking, is excellent in water resistance, water whitening resistance, blocking resistance, heat resistance, solvent resistance, adhesion and hardness. The external clear varnish, the stone finish finishing binder, the top coat, the OP varnish, etc., which has a good workability in which the surface dryness of the film can be appropriately adjusted and which is easy to handle without gelling, The present invention relates to an aqueous crosslinkable resin composition that can be advantageously used as a printing ink, an adhesive, a fiber processing agent, and the like.

[0002]

2. Description of the Related Art Aqueous crosslinkable resin compositions prepared by blending an aqueous dispersion of a carbonyl group-containing copolymer resin with a hydrazine derivative having at least two hydrazino groups in the molecule have been known (for example, Japanese Patent Application Laid-Open No. 2000-242242). JP-A-57-3850, JP-A-64-48801 and the like).

Such an aqueous crosslinkable resin composition can be easily crosslinked at room temperature to form a film excellent in various physical properties, but since the surface drying rate of the resin composition after coating is too fast, it can be spliced. There is a problem that unevenness and shrinkage cracks easily occur in the dried coating film. In order to improve these drawbacks, it has been attempted to use a large amount of an emulsifier, add a wetting agent, a water-soluble resin, or the like. However, in either case, the water resistance of the film is reduced, and it is not put to practical use.

On the other hand, in order to improve water resistance, there are a method of further adding an epoxy group-containing compound and a method of using an epoxy group-containing monomer as a monomer constituting an aqueous resin dispersion. Then, although the water resistance of the coating is improved, since an epoxy group is used, gelation is likely to occur, and it is usually necessary to use two liquids, and there is a problem that handling is complicated.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to improve the above-mentioned drawbacks of the conventional carbonyl group-containing copolymer resin aqueous dispersions containing a hydrazine derivative, and in other words, it is easy to achieve at room temperature. After crosslinking, it gives a film excellent in water resistance, water whitening resistance, blocking resistance, heat resistance, solvent resistance, adhesiveness and hardness, and the surface dryness of the film can be adjusted to a suitable level. It is intended to provide an aqueous crosslinkable resin composition which has workability and is easy to handle without gelation.

[0006]

As a result of various studies to solve the above problems, the present inventors were able to achieve the above object by adopting the following constitution.
That is, the aqueous crosslinkable resin composition of the present invention comprises (A)
A carbonyl group-containing resin aqueous dispersion composed of resin particles having a structure of two or more layers containing a carbonyl group in at least the outermost layer, (B) a hydrazine derivative having at least two hydrazino groups in the molecule, and (C) an epoxy group An aqueous crosslinkable resin composition comprising an epoxy group-containing compound containing at least 2 in the molecule, wherein 5% by weight or more of the outermost layer of the resin particles of the carbonyl group-containing resin aqueous dispersion is solubilized. And 4 to 50% by weight of the whole particles are solubilized.

The resin of the carbonyl group-containing resin aqueous dispersion (A) in the present invention has at least a two-layer structure, and the resin having a carbonyl group in the outermost layer thereof may be used. (A) a carbonyl group-containing monomer having at least one aldo group or keto group and one polymerizable unsaturated double bond in the molecule, and (b) an ethylenic monomer Saturated carboxylic acid, (c) 20
A monomer having a solubility in water at 8 ° C of 8 g / 100 ml or less, and (d) other unsaturated monomer are appropriately combined to improve the physical properties by solubilization and balance the physical properties such as water resistance. It is preferable in terms of keeping.

Examples of the monomer (a) for preparing the resin aqueous dispersion (A) include acrolein, diacetone acrylamide, formyl styrene, a vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl). Methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), general formula

[0009]

[Chemical 1]

(In the formula, R ¹ is H or CH ₃ , R ² is H or an alkyl group having 1 to ³ carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms, and R ⁴ is 1 to 1 carbon atoms. Acrylic (or methacryl) oxyalkylpropenal represented by 4 alkyl groups), diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-
Hydroxypropyl acrylate acetyl acetate,
Examples thereof include butanediol-1,4-acrylate acetyl acetate. Particularly preferred monomers thereof are diacetone acrylamide, acrolein and vinyl methyl ketone. Two or more kinds of these monomers may be used in combination.

The monomer (a) is an essential component for the preparation of the present resin aqueous dispersion (A), and its amount is preferably 0.5 out of all the monomers constituting the resin particles. weight%
As described above, the content is more preferably 2 to 30% by weight. If the proportion of the monomer (a) used is too low, the crosslinking reaction with the hydrazine derivative will not be carried out sufficiently, and improvement in water resistance cannot be expected. If the proportion of the monomer used is too high, the physical properties will be in proportion to the amount. Not only is not seen, but the film obtained from this composition becomes brittle and is not suitable for practical use.

The monomer (a) may be contained in either the inner or outer layer of the resin particles of the resin aqueous dispersion of the present invention, but it is always necessary in the outermost layer, and further, both the inner and outer layers. From the viewpoint of water resistance of the film, it is more preferable that the water content is included.
In the outermost layer, 0.5 of all monomers constituting the outermost layer is used.
It is preferably at least wt%, particularly preferably 2 to 20 wt%. Further, in the inner layer, 0.5% by weight or more, and particularly preferably 1 to 15% by weight, of all monomers constituting the inner layer are preferable.

The monomer (b) for preparing the aqueous resin dispersion (A) may be a monocarboxylic acid or a polycarboxylic acid, but preferably 3 to 5 It is a mono- or di-olefinically unsaturated carboxylic acid having carbon atoms. In particular, acrylic acid, methacrylic acid, and itaconic acid are preferable. The amount of the monomer (b) used is 0.5% by weight or more, preferably 2 to 40% by weight of all the monomers constituting the outermost layer in the outermost layer, and the inner layer in the inner layer excluding the outermost layer. It is preferably less than 4% by weight of all the monomers constituting the.

If the amount of the same monomer in the outermost layer is too small, sufficient solubilization (water solubilization) cannot be performed when the solubilization treatment is performed by adding an alkali and / or organic solvent, and the film is formed. No sufficient smoothness, adhesion, gloss, and water whitening resistance can be obtained. On the other hand, if the amount of the monomer is too large, the water resistance of the film is reduced, and the adhesion to the coated object is reduced. Further, if the amount of the same monomer in all the monomers constituting the inner layer except the outermost layer is too large, the problem of deterioration of water resistance will occur, which is not preferable.

The monomer (c) for preparing the aqueous resin dispersion (A) is a monomer copolymerizable with the monomers (a) and (b), and is in water at 20 ° C. Solubility in 8
g / 100 ml Water or less monomer. Specific examples thereof include acrylic acid or methacrylic acid ester of a saturated alkanol having 1 to 10 carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-
Ethylhexyl acrylate; vinyl aromatic compounds such as styrene; vinyl halides such as vinyl chloride and vinylidene chloride; unsaturated hydrocarbons such as ethylene and butadiene; vinyl esters such as vinyl acetate and vinyl propionate; other acrylonitrile, methacrylonitrile,
Examples thereof include glycidyl methacrylate.

The amount of the monomer (c) used in the outermost layer is 30 to 99% by weight, preferably 55 to 94% by weight, based on the total monomers constituting the outermost layer, and in the inner layer excluding the outermost layer. Is preferably 80 to 99.5% by weight based on the total monomers constituting the inner layer. If the amount of the same monomer in the outermost layer is too small, the water resistance is reduced or the coating becomes brittle, and if the amount of the same monomer is too large, the water resistance is reduced or the substrate adhesion is reduced. . If the amount of the same monomer in all the monomers forming the inner layer except the outermost layer is too small, the water resistance is lowered or the film becomes brittle.

The monomer (d) for preparing the resin aqueous dispersion (A) is a monomer other than the above-mentioned monomers (a) to (c), and is, for example, Unsaturated amides such as acrylamide and methacrylamide; hydroxyl group-containing monomers such as hydroxyethyl acrylate and hydroxypropyl acrylate; sulfonated monomers such as vinyl sulfonic acid, styrene sulfonic acid, and salts thereof; other N-methylol acrylamide And so on.
(D) The amount of the other unsaturated monomer is 0 to 69% by weight, preferably 0 to 15% by weight of the total amount of unsaturated monomers constituting the resin particles.
% By weight.

The monomer (d) is not an essential component in both the outermost layer and the inner layer, and if the amount used is too large, the hydrophilicity of the resin particles obtained will be too high. The water resistance of the resulting coating is reduced. As a method for producing a resin aqueous dispersion (A) of resin particles having at least a two-layer structure using each of the above monomer mixtures,
The monomer mixture forming the inner layer is previously polymerized in water to be an emulsion state, and then the monomer mixture forming the outermost layer is added and emulsion-polymerized.

For emulsion polymerization of the monomer mixture constituting each layer, there may be used a method of carrying out polymerization with a water-soluble polymerization initiator using an emulsifier, a method of carrying out polymerization by soap-free polymerization, or the like. Examples of the emulsifier include various anionic, cationic and nonionic emulsifiers, and further polymeric emulsifiers. A particularly preferred emulsifier is a carbonyl group-containing polymer emulsifier described in JP-A-64-48801, which is a publication of a patent application relating to the invention of the present inventors (a part).

The polymerization initiator used in emulsion polymerization is preferably an inorganic peroxide such as potassium persulfate, ammonium persulfate or hydrogen peroxide. These inorganic peroxides include
You may use it together with a reducing agent as a redox initiator. Various methods can be used as a method for supplying the monomer in the emulsion polymerization. For example, various methods such as a batch charging method, a monomer addition method and an emulsion addition method can be used. Further, a seed polymerization method in which the composition of the monomer to be added is sequentially changed, a power feed polymerization method, or the like can also be used. When such a method is used, the center portion of the produced copolymer resin particles and the outside can be The copolymer composition can be varied to control the degree of solubilization.

A chain transfer agent is preferably used in the emulsion polymerization. This is because the copolymer resin generally obtained by emulsion polymerization has a high molecular weight, and therefore, when it is solubilized in water by addition of an alkali and / or an organic solvent, it is difficult to achieve sufficient solubilization. This is because when the transfer agent is used, the molecular weight of the produced copolymer resin can be reduced and the solubilization is facilitated.

Therefore, it is effective to add it when polymerizing the outermost layer component. The amount of chain transfer agent used is 0.01 based on 100 parts by weight based on the total amount of monomers in the layer.
-3 parts by weight is preferred. The chain transfer agent used is
Any chain transfer agent that is commonly used in the polymerization and copolymerization of vinyl monomers and the like may be used. Specific examples thereof include methyl mercaptan, t-butyl mercaptan, decyl mercaptan, benzyl mercaptan, lauryl mercaptan, stearyl mercaptan,
Mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoacetic acid and mercaptopropionic acid; alcohols such as methanol, n-propanol, isopropanol, t-butanol, benzyl alcohol and allyl alcohol; hydrocarbons such as ethylbenzene and cumene Kinds; halogenated hydrocarbons such as chloroethane, chloroform, carbon tetrachloride, carbon tetrabromide and the like.

The outermost layer of the resin particles of the resin aqueous dispersion (A) prepared by the emulsion polymerization described in detail above has a solubilization rate of the resin of 5% by weight or more, preferably by addition of an alkali and / or an organic solvent. Is solubilized so as to be 15% by weight or more, and 4 to 50% by weight, preferably 5 to 35% by weight of the whole particles are solubilized.

When the resin particles have a three-layer structure or more, the outermost layer is called the outermost layer, and the other two inner layers are called the inner layer. The solubilization rate of the inner layer is 5 times that of the outermost layer.
The solubilization rate of the whole particle is 4 to 50% by weight,
However, less than 30% by weight, preferably 0.3-25
It is desirable to set it as the weight%.

If the solubilization rate of the entire particles is too low, the adhesion and gloss of the coating film obtained from the composition on the substrate will be lowered, and conversely, if the solubilization rate of the entire particles is too high, the coating obtained will be large. The water resistance of the membrane is reduced. The solubilization treatment (that is, addition of an alkali and / or an organic solvent) may be performed before the initiation of polymerization for producing an aqueous resin dispersion,
It may be during the polymerization. In any case, the "solubilization rate" described in the present specification means the solubilization rate measured by the following method.

A solubilization treatment was carried out under exactly the same conditions as the solubilization treatment actually carried out except that no hydrazine derivative or the like was added to prepare an aqueous resin dispersion, and the obtained aqueous resin dispersion had a nonvolatile content of 15% by weight. % After diluting with water to
The diluted solution was centrifuged at a centrifugal acceleration of 1.8 × 10 ⁵ g for 60 minutes, and the nonvolatile content in the obtained supernatant was measured to measure w
The solubilization rate represented by the following formula is defined as the weight part, and the non-volatile content in the diluent used for centrifugation is measured to be W weight part.

Solubilization rate = w / W × 100 (wt%) Therefore, for example, copolymerization by adding an alkali and / or an organic solvent to the polymerization system before or during polymerization for producing an aqueous resin dispersion. When the solubilization rate of the polymerized product containing the copolymer resin obtained by the polymerization is already 5% by weight or more as it is, It is not necessary to add alkali and / or organic solvent for the treatment.
The solubilization rate of the outermost layer or each layer of the inner layer excluding the outermost layer components is the same as the monomer constituting each layer under the same conditions as those for preparing the resin particles of the resin aqueous dispersion (A) used in the present invention. Only the mixture is polymerized and defined by the method detailed above.

The alkali used for the solubilization treatment is an inorganic water-soluble alkali such as sodium hydroxide or potassium hydroxide; or an inorganic salt which shows alkalinity when dissolved in water, such as sodium hydrogen carbonate or pyrophosphate. Sodium and the like; other examples include aqueous ammonia and organic amines. Addition of alkali is as described above.
It is not always necessary to carry out after the polymerization of the resin aqueous dispersion, and in some cases, the copolymerization may be carried out after adding an alkali to the monomer before the polymerization to neutralize it. The amount of alkali used may be an amount that completely neutralizes the carboxyl groups in the copolymer resin or an amount that partially neutralizes the carboxyl groups.

The organic solvent used for the solubilization treatment may be supplementarily added when it cannot be sufficiently solubilized in water by only adding an alkali, or may be solubilized by adding only the organic solvent. The organic solvent used is not particularly limited, but includes texanol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether and their acetates, benzyl alcohol, butyl carbitol acetate, 2,2,4-trimethyl-1,3.
-Pentanediol and the like.

The composition of the present invention comprises a hydrazine derivative having at least two hydrazino groups in the molecule and at least two epoxy groups in the molecule in the resin aqueous dispersion (A) prepared as described above. The epoxy group-containing compound contained therein is added. Examples of the hydrazine having at least two hydrazino groups in the molecule include 2
A dicarboxylic acid dihydrazide having 10 to 10, especially 4 to 6 carbon atoms (for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, Itaconic acid dihydrazide), an aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms (eg ethylene-
1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine and the like).

Further, the general formula,

[0032]

[Chemical 2]

(In the formula, X is a hydrogen atom or a carboxyl group, Y is a hydrogen atom or a methyl group, A is each unit of acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester or maleic anhydride. , B is a unit of a monomer copolymerizable with acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester or maleic anhydride, and k, m and n are the following formulas 2 mol% ≤ k ≤ A polymer represented by 100 mol% 0 mol% ≦ (m + n) ≦ 98 mol% (k + m + n) = 100 mol% is also used as the hydrazine derivative. Such polymers are described in detail, for example, in JP-A-55-6535.

Examples of the epoxy group-containing compound containing at least two epoxy groups in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether and propylene. Examples thereof include polyglycidyl ethers of polyhydric alcohols such as diglycidyl ether and polypropylene glycol diglycidyl ether, glycidyl ether alicyclic epoxy resins of bisphenol A, nitrogen-containing epoxy resins, polybutadiene type epoxy resins, and urethane-modified epoxy resins.

The aqueous crosslinkable resin composition of the present invention comprises the above-mentioned (A) carbonyl group-containing resin aqueous dispersion, (B) hydrazine derivative and (C) epoxy group-containing compound. Component (C) is 0.1 to 100 parts by weight, preferably 0.3 to 60 parts by weight, based on 100 parts by weight of the solid content of the component). If the proportion of the component (C) is too small, the physical properties of the resulting coating film are not sufficiently improved,
If the amount is too large, the product becomes sticky or gels, resulting in poor handleability.

The component (B) has a ratio of the aldo group, keto group and epoxy group to the hydrazino group contained in the composition,
The molar ratio is 0.2 to 8 mol, preferably 0.5 to 4 mol. If the proportion of hydrazine derivative is too low,
Since cross-linking between resins is not performed sufficiently, improvement in water resistance cannot be expected, and even if the ratio is too large, not only the effect of improving water resistance commensurate with it cannot be obtained, but also the film is formed. It is opaque and becomes brittle, and on the contrary, the crosslinking effect is reduced.

In the present invention, various synthetic resin emulsions, synthetic rubber latices, modifiers such as various tackifiers, extenders such as inorganic fillers, thickeners or viscosity modifiers, antifoaming agents and the like are added to the present invention as required. I can.

[0038]

[Examples] Hereinafter, examples and comparative examples will be described in detail. The "parts" and "%" described in these examples are on a weight basis. Example 1 Temperature controller, anchor type stirrer, reflux condenser, supply container,
After the inside of the reaction vessel equipped with a thermometer and a nitrogen introducing tube was replaced with nitrogen, the following composition was charged therein.

Water 35 parts 35% aqueous solution of sulfuric acid half ester sodium salt of p-nonylphenol with 20 mol of ethylene oxide (referred to as “anionic emulsifier A”) 1.8 parts P-nonylphenol with 25 mol of ethylene oxide (“nonionic The following mixtures were prepared as feeds I, II and III separately for 2 parts of a 20% aqueous solution of "emulsifier B").

Feed I Water 35 parts 35% aqueous solution of the above anionic emulsifier A 3.7 parts 20% aqueous solution of the above nonionic emulsifier B 3.5 parts Styrene 37.5 parts Butyl acrylate 37.1 parts Diacetone acrylamide 4.0 parts Acrylic acid 0.4 parts Feed II water 8 parts 35% aqueous solution of the above anionic emulsifier A 0.8 parts 20% aqueous solution of the above nonionic emulsifier B 1.05 parts Styrene 1 .5 parts Methyl methacrylate 3.6 parts Butyl acrylate 13.9 parts Diacetone acrylamide 1.0 parts Acrylic acid 1.0 parts t-Dodecyl mercaptan 0.2 parts Feed III water 12 parts Potassium persulfate 0.5 Department

Add 10% of Feed I into the reaction vessel and add 8
Heat to 5 ° C. and then charge 10% of Feed III into the reaction vessel. After a 10 minute hold, Feed I was added over 3 hours and Feed II was added over 1 hour at 1 hour intervals. Feed III is the feed from the beginning of addition of Feed I
It was continuously and uniformly fed until the addition of II was completed. After the addition was completed, the mixture was kept at 90 ° C. for 1.5 hours, and then the emulsion polymerization was completed to obtain an aqueous resin dispersion liquid having a nonvolatile content of about 50%. Ammonia water is added to the obtained dispersion liquid to adjust the pH to 9.3,
Furthermore, 6 parts of benzyl alcohol as an organic solvent and 25.7 parts of a 20% solution of adipic dihydrazide,
2.6 parts of ethylene glycol glycidyl ether was added, and further water was added so that the viscosity became 5,000 to 8,000 cps to obtain an aqueous crosslinkable resin composition. In addition,
The solubilization rate of the outer layer component was 95%, and the solubilization rate of the entire particle was 11.3%.

Examples 2 to 6 and Comparative Examples 1 to 6 Examples were carried out except that the types and amounts of the monomer composition, alkali, solvent, hydrazine derivative and epoxy group-containing compound were changed as shown in Tables 1 and 2. An aqueous resin composition was prepared in the same manner as in Example 1. The amount of water and each emulsifier in the feed was distributed to each of the inner layer and the outer layer according to the weight of the monomer mixture.

[0043]

[Table 1]

[0044]

[Table 2]

* 1 ADH ... 20% aqueous solution of adipic dihydrazide [Evaluation of physical properties] The aqueous resin compositions obtained in the respective Examples and Comparative Examples were evaluated by the following methods.

Appearance of coating film: 20 ° C, 60% RH
In a temperature-controlled room at a doctor blade on a glass plate
It was applied so as to have a thickness of 00μ, dried for 5 days in a place where it was not exposed to wind, and the presence or absence of abnormality was judged by visual observation and finger touch. The state was specular and colorless and transparent, and the state in which there was no extract on the surface was normal, and the others were abnormal. In that case, the state was noted.

Water whitening resistance: A sample piece similar to the above sample piece for appearance measurement was prepared and immersed in a constant temperature water bath at 20 ° C. and 40 ° C. with an upward inclination of 70 ° and immersed for 7 days to change the whitening state of the coating to a color tone. It was evaluated by. It should be noted that the evaluation levels are colorless, light blue, bluish white, and white, which are bad.

Toluene swelling ratio: Pour onto a Teflon-lined glass plate so that the film thickness after drying would be about 500 μ.
It was dried at 0 ° C. for 7 days. Incidentally, on the 5th day on the way, it was peeled off from Teflon and turned inside out and dried. This coating was punched out into a 5 cm × 5 cm square test piece. The test piece was immersed in toluene at 20 ° C., soaked for 24 hours, taken out, and the length of the side was measured with a caliper to obtain the value from the following formula. Toluene swelling ratio (%) = {(after dipping-before dipping) dimension / dimension before dipping} × 100

Water absorption rate: A test piece similar to the above-mentioned sample piece for measuring the toluene swelling rate was prepared and immersed in a constant temperature water bath at 20 ° C. for 2 days. Then, the water content on the surface was quickly removed and precisely weighed to absorb water. I asked for the rate.

The results are shown in Tables 3-4. Further, 0.5 part of a defoaming agent (trade name, manufactured by San Nopco Co., Ltd.) per 100 parts by weight of the solid content of the aqueous crosslinkable resin composition of the present invention
Foamaster AP), 320 parts of ceramic sand (100m
es) and 80 parts of cold water (trade name of Copper Wa Mining Co., Ltd.
KD 50 mesh) was added to prepare a paint, which was also evaluated by the following method. The results are also shown in Tables 3-4.
It was shown to.

[0051]

[Table 3]

[0052]

[Table 4]

[Evaluation of Paint] Roller transferability: 100 g / m ² (wet) of a solvent-based sealer (Kikusui Chemical Co., Ltd., trade name Kikusui Primer BS) on a flexible plate of 300 × 450 mm in advance.
And a dried panel was prepared, and the paint compounded with a striped roller for exterior material was applied to 1.5 kg / m ² . After drying for another 5 minutes, the same roller was used to reapply the 1/3 surface, and the striped pattern was evenly applied. Excessive winding of the coating material on the roller, unevenness of the prominent pattern at the splicing part (sagaku, fault, etc.), ○, ○ ~ △,
The evaluation was made in three grades.

Touch-drying time: The dry state of the coated surface is 2
The surface wetting disappearance time (minutes) was determined by touching the finger every minute.

Appearance of coated surface: The coated plate was dried at 20 ° C. for 7 days, and the appearance was evaluated by finger touch and visual observation. Those with no occurrence of slime, dry shrinkage cracks, etc. were regarded as normal, and the others were regarded as abnormal, and abnormal ones were marked with the state.

Warm water whitening resistance: 100 g / m ^{2 of a} solvent type sealer (Kikusui Chemical Co., Ltd., trade name Kikusui Primer BS) was previously applied to a 70 × 150 mm flexible plate.
Prepare a coating applied so that it becomes (wet), attach a frame with a thickness of 2 mm to the plate, apply the blended paint with a spatula and apply evenly with a thickness of 2 mm with a trowel, and apply at 20 ° C. In 5
It was dried for a day to give a test piece. On the 4th day of drying, seal the back and sides with wax and place in a constant temperature water bath at 40 ℃.
It was immersed for a day and the whitening state was evaluated. The evaluation standard was the same as the water whitening resistance in the physical property evaluation.

Warm water softening resistance: A test piece similar to the above-mentioned test piece used for hot water whitening resistance measurement was prepared, immersed in a constant temperature water bath at 40 ° C. for 7 days, and scratched with nails for evaluation. "○" My nails do not stand. “○ ～ △” My nails come in but it doesn't collapse easily. "△" is fragile

Blocking resistance: A test piece similar to the test piece used for the above-mentioned hot water whitening resistance measurement was prepared and placed in a constant temperature bath at 50 ° C. Graft paper was sandwiched with a weight of 40 mmφ × 500 g on the test piece and pressure-treated for 24 hours. After the treatment, the weight was removed, the mixture was allowed to stand at 20 ° C. for 3 hours, and then the peeling of the graft paper was evaluated. “○”… Peels off almost without any sound. “○ ～ △”… Has more than half adhered, but it requires less force to remove and produces less sound. "△" ... It adheres to the entire surface, it takes a lot of force to peel it off, and the sound is loud.

[0059]

EFFECTS OF THE INVENTION The aqueous crosslinkable resin composition of the present invention easily undergoes a crosslinking reaction at room temperature, and after crosslinking, has water resistance, water whitening resistance,
Provides a film with excellent blocking resistance, heat resistance, solvent resistance, adhesiveness and hardness, and has a good workability that allows the surface dryness of the film to be adjusted appropriately, and is easy to handle without gelation. Is.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Reference number in the agency FI Technical indication C09J 201/02 JBC 7415-4J (72) Inventor Takeshi Awada 1000 Kawajiri-cho, Yokkaichi-shi, Mie Mitsubishi Oil (72) Inventor Ryutaro Hayashi, 1000, Kawajiri-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Badishe Co., Ltd.

Claims (2)

[Claims] 1. (A) A carbonyl group-containing resin aqueous dispersion comprising resin particles having a structure of two or more layers containing a carbonyl group in at least the outermost layer, and (B) having at least two hydrazino groups in the molecule. An aqueous crosslinkable resin composition comprising a hydrazine derivative and (C) an epoxy group-containing compound containing at least two epoxy groups in the molecule, which is the outermost layer of resin particles of the carbonyl group-containing resin aqueous dispersion.
% By weight or more is solubilized, and 4 to 50 of the whole particles
An aqueous crosslinkable resin composition, characterized in that it is solubilized in a weight percentage. 2. The aqueous crosslinkable resin composition according to claim 1, wherein the solubilization rate of the inner layer excluding the outermost layer of the resin particles of the carbonyl group-containing resin aqueous dispersion is less than 30% by weight.